Terpene-cyanoacyl compound and method of producing same



v Patented Oct. 8; 1940 I I I r 2,217,615 I TERPENE CYANOACYL ooMPoUNnA'Nn 1MET HQD- QEPR,0DUCING Jose h-"N. onn e, Wilmingtom"DeLJ aSsignor to "j Hercules Powder company wilming'tjoniDeL, a corporatiox'ifoifDelawar I:

; UNITED f No Drawing, Application in @227, 1939; I .7 "seria1No.311,170," v

r -415 Claims-l (01. 260 454) 1 V i This invention relates tola newseries of terpene acid, a chlorovaleric, acidga chlorocaproi acid, compounds and morepart'icularly to-a'newseries j, chlorob'enzoic, acid, jchlorolauric .acid,[ chloroof terpene compounds havingthe type formula *myristictacid chlorostearicacidgchloroleic acid, ROOCRXCN-inw'hich; R isflthe terpenew alcohol chlororicinoleic acid, chlorobe cnlcgacli o o q formed when, allo ocimene-is condensed with erucic acid; chloromaloni cidfand .chloro- 5 croton-aldehydeand thecondensate reduced, in lphthalic'acid,etcQandthec respondingjbromine which R" isan aliphatic or, aromatic radical, and 'andl iodin'e substitutedjacidsi Mixtures may be in Whl'Ch X is a member of the groupconsisting used if desired., Acid-fianhydri v es-or.ac${l ;halides of sulfur, selenium, and tellurium Italso re such as, for example; aslthose"corresponding to 10 lates to a method forQthe preparationof these gthe acids hereinabove nam d are also suita 1 o d I 1 j al en sub tit edacylating a ent's; By the method in accordance with this invenr ,Themetalthiocyanatewhi'chfl use may' be any tion, I startwith a' terpeneealcohol formed b ;(m tal-thiocyana-teJ-wh ch 11s r iv guderlt condensing allo-ocimenejwith crotonaldehyde t O0l'1d i; l fi p fi blactive under the 15 and subsequently reducing lthecondensate. I vconditions p qy g i-,m'u tfbepartial y or-com react this alcohol'withasuitab1e' halogen subpletely soluble vin the reaction jmixt r I i stituted acylating agent and then with a metal. S a metal i aha fo "exam ar thiocyanate, a metal selenocyanate, or a metal Y i th y na DQ th y n tellurocyanate which is reactive under the conc n e al iumitmocyana animen um l 2o ditions employed. r 1 io t he hcn' sflde n ito ak th m The reduced allo-ocimenecrotonaldehyde con terpene selenocyanateytthe metaltselei'ztocye' nate densate whieh'r employ in my invention maybe m y use, may e for e a p e,"v dilim t l mprepared by condensing aIId-ocimehe 'withcro-jf C a D iwn selenocyanate,glithium Selene-' tonaldehyde' as describedin' Ber.-' 68, 1435-8 an e ammonium c Y teM a c m" (1935) byB. Arbusot and reducing the resulting elen cyanat'e e c". a d s m larl atheme l 725 aldehyde to an alcohol, For conveniencefthe u a eh wlma r ma eh o k terpene alcohol so producedwillbe referredio" le um enda;P as um' l mhereinafter as a reduced :allo o'cimene crotone ag h umi c an e a m ldehyde co densate. Thereduction'jmay-for mc n t t :"1 example-be carried-out conveniently hy -h drc --'-Ih a9ti n;1n qrda ew h i is i iqn genation of the primaryvcondensate, or "treat-"i ll e abl i eparr e 91m e; '5 ment with sodium and alcohol,*etcl"'I'he result -r u d 1 w men wn de e; o d a e;

ing alcohol maybe saturated or unsaturated ac i l; fir 9 rm tha U I E H W QI cording to the extent of the h ydrog enatich' i .L WI ma em n r sultiug-haloge a gd; Catalytic hydrogenationfof the n's tu'ratedhide W1e te th en? fi lm l efi iim es :f hyde m'ay'be' accomplished using catalysts such the yrnmduc 4 1f 1 -n3 i ablytal l ""asRaney nickel, or other nickelcatalyst, or eepacidic material is OVEd, e'l helse cond stageioif' v per chromite. Temperatures of' fr'o'm aboutYfifl h reaction h tr 4 pf-this halogenated to about 250C. and pressures-of from about-I00 3Cyl ester of the fi rbe d with the 1 4otd about'5000 lbs/sq. in. may beemployed. in -,m anatm l c n h r .t roiaddition to'the reduction of'the aldehyde -group]v cyanateas thecase ay b fif llowedeby'rercoyery i tof'a primary alcohol group, the ,usebf{:Ran;v "0 hC'D Q pret r' to,carryout.1the, ,seccnd, I nickel catalyst causes'hydrognationbi the-don "nyeeenf e o 'z i b n rt sol ,ent'- V ble bonds in th'e'remainder of the-moleculeand" ch} r o am methanol, X QJwP Q-F I '7 1;; -4 the product is thus asaturated alcohoL-j-lf-cop' D Lv r-. aieihylacet e t eEa hp l 4 tr'per chromite catalyst is used, .it 'is boss'ible-toe-ste s. may e a ueda t atwan 'ztexnne atu e 'hydrogenate onlythe aldehyde group"andi-f the' "withintherange;of-ga lpoutslyyc. to about 25QjC product is anfunsaturated alcohol containing' 'one f p e a y t f he m i lqpub'fi -"pe or two'double bonds.

.9?,toaboutZQO? (3,, "'50 The halogen-substituted acylflti g agehtiwhich Ahalogenated-Emilyreact-With thqa-lcqh 1450' d I use may be such an acid as, for example,- mono: from the allo-ocim-ene crotonaldehyd r q t chloracetic' acid, dichloroaceticnacid; trichloro-J "at onegor more reaqtivepositions. ,rIt" ay acetic acid, alpha-chloropropionic acid, beta; withadouble bondf-Whtirgthe'cohdm chloropropionic acid, alpha-chlo'robutyric;acid, saturated:or-itmay-reactwith hyt '55 beta-chlorobutyric acid, 'gamma-chlorobutyr ic 1 Thus, .theproductaccordin reaction mixture was may contain one or more thiocyano ester groups for each molecule of the reduced allo-ocimene crotonaldehyde condensate, and it will be appreciated that the sulfur content of the product may vary accordingly. In referring to thiocyanoacyl esters herein and in the claims, the esters mentioned include-both mono and poly esters or mixtures thereof. An acyl halide or anhydride reacts only at hydroxyls and usually does not react at a double bond directly.

The halogen substituted acylates of the first stage reaction are light in color if the reaction is carried out in the absence of oxygen, for example, under a blanket of CO2. Substantially water white esters may be obtained by vacuum distilla tion. The color of the thiocyanoacylate products follows the color of the first stage ester from which they are prepared. Where very lightcolored products are desired and where it is desired to insure products of no odor or minimum odor, the first stage reaction maybe conducted, if desired, in a non-oxidizing atmosphere, or the first stage product may be vacuum distilled, or both these measures may be taken.

The-method in accordance with this invention will be further illustrated by the examples which follow. All parts and percentages herein are by weight unless otherwise specified.

Erample 1 I A mixture of 138 partsof the saturated alcohol prepared by hydrogenation of' allo-ocimene crotonaldehyde condensate and 138 parts of monochloroacetic acid was heated toa temperature of 1'70 to 180 C. under a blanket of carbon dioxide for 8 hours. The water formed in the reaction was allowed to distill off through an 18 inch Hempel column; 'The reaction was continued for an additional 8 hours at 180 to 200 C. The resulting reaction mixture was then washed with water until acid free. A yield of 148 parts of material analyzing 9.1% chlorine and containing the chloroacetate of the above alcohol, was recovered.

A mixture of-142-parts of this chloroacetate product, parts of potassium thiocyanate, and 160 parts of ethyl'alcohol was refluxed for 12 hours; To the reaction mixture, there was added approximately parts of petroleum ether. This mixturewasthen water washed, removing alcohol and any'unreacted thiocyanate. The petroleum ether was then evaporated off at reduced pressure leaving 140 parts of product having a; sulfur content of 22% and containing the' thiocyanoacetate of the saturated alcohol prepared by hydrogenation of the allo-ocimene crotonaldehyde condensate.

, Example 2 s A mixture of 146 parts of the unsaturated alcohol prepared by the partial hydrogenation of alloocimene crotonaldehyde condensate and 146 parts of monochloi-oacetic acid was heated for 8 hours at 1'70 to 180 C. under a blanket of carbon dioxide. The waterformed by the reaction was allowed to'distill off through an 18 inch Hempel column. The reaction'was then continued an additional 8 hours at 180 to 200 C. After this, the washed with water until acid free. A yield of 141 parts of chloroacetate ester analyzing 6.25% chlorine was obtained.

A mixture of 136 parts of this chloroacetate, 80 parts of potassium thiocyanate, and approximately parts of 95%- ethyl alcohol was refiuxed for 12 hours. To the resulting mixture there was added approximately 140 parts of petroleum ether. and the mixture obtained was then washed several times with water. The petroleum ether was evaporated under reduced pressure. A yield of 141 parts of product, analyzing 4.25% sulfur, and containing the thiocyanoacetate of the unsaturated alcohol prepared by hydrogenation of the allo-ocimene crotonaldehyde condensate, was thus recovered.

Example 3 A mixture of 25.parts of the unsaturated alcohol prepared by partial hydrogenation of an alloocimene crotonaldehyde condensate and 40 parts of alpha-chloropropionic acid was heated under reflux for about 8 hours at 160 to C. with a stream of carbon dioxide passing through the flask and condenser to remove water formed. The reaction mixture was water washed until acid free, and to aid in the separation of the product about 35 parts of petroleum ether were added. After separation from the water, the petroleumether was removed from the product by evaporation on the reduced pressure. 'Twentynine parts of liquid chloropropionate of the above alcohol, analyzing 6.2% chlorine, was recovered.

A mixture of 22.5 parts of this chloropropionate, 10 parts of commercial sodium thiocyanate, and about 28 parts of 95% ethyl alcohol was refiuxed for about 4 hours. There was added to the reaction mixture about 35 parts of petroleum ether and the resulting. mixture was then given 5 water washes, after which a test showing that all inorganic thiocyanate had been removed. The petroleum ether was then removed by evaporation under reduced'prcssure. A yield'of 23 parts of liquid, which analyzed 1.1% chlorine and 4% sulfur, and contained the alpha-thiocyanopropionate of the terpene alcohol initially reacted, was recovered.

Example 4 I A mixture of 25 parts of the saturated alcohol prepared by hydrogenation of allo-ocimene crotonaldehyde condensate, 30 parts of alpha-bromon-butyric acid was heated, under reflux for about 8 hours at 160 to 165 C. with a stream of carbon dioxide passing through the reaction mixture to remove water formed. About 35 parts of petroleum ether was added to the resulting reaction mixture which was then water washed until free of acid. .The petroleum ether was removed by evaporation under reduced pressure. Ayield of 3'? parts of liquid bromobutyrate ester, which analyzed 17.5% bromo, was obtained. A mixture of 34.2 parts of this bromobutyrate, 15 parts of sodium thiocyanate, and about 40 parts by weight of 95% ethyl alcohol was refluxed for about 4 hours. ,About 35 parts of petroleum ether was then added and the resulting mixture was washed with water to remove all alcohol and unreacted sodium thiocyanate. The petroleum ether was then evaporated under reduced pressure. A yield 0E 30.5 parts of liquid alpha thiocyano-n-butyric a id ester ofhydrogenated,allo-ocimene crotonaldehyde condensate having a sulfur content of 6.9% was thus obtained. p

The products of the examples contain unesterified terpene compounds and petroleum hydrocarbons in varying proportion. A certain portion of the original reactant is usually not esterified and, in addition, there maybe some conversion of esters to terpene hydrocarbons in. the second stage. The unesterified terpene compounds and petroleum hydrocarbons may be removed by vacuum distillation or vacuum steam distillation if desired. However, such removal is in general of no advantage since the products of this invention are conveniently utilized in diluted form for most purposes and since the diluents mentioned are in most cases colorless and of pleasant or 5 slight odor. Similarly, complete removal of petroleum ether or other inert solvent from the product is usually unnecessary. However, I prefer to remove excess metal thiocyanate, selenocyanate, or tellurocyanate, and any other water 10 by thorough washing of a petroleum ether solu tion with water.

The compounds according to this invention are useful in insecticides. For example, they may be 15 used in kerosene solution in a concentration between about 0.5% out other toxic agents suchas pyrethrum and rotenone, as contact spray insecticides, or in emulsions, or on solid carriers. The compounds are also useful as flotation agents in the concentration of minerals. They may also be used as intermediates for the preparation of other compounds, such as, for example, wetting agents by treatment with an oxidation agent such as nitric 35 acids. Many of the compounds possess wetting power without modification.

The term aromatic any radical containing structure.

This application is a continuation-in-part of my previous application, Serial No- 198,687, filed March 29, 1938, entitled, Terpene cyanoacyl compounds andmethods of producing same.

It will be understood that the details and exa benzene linkage in its allo-ocimene crotonaldehyde condensate, in which R is a radical selected from the group consisting of aliphatic radicals and aromatic radicals, and

4| in which X is a member of the group consisting of sulfur, selenium, and tellurium.

2. Aterpene compound having the type formula ROOCR'SCN in which R is a radical of a reduced allo-ocimene crotonaldehyde condensate and in V v 0 which R is a radical selected from the group consisting radicals.

3. A terpene compound having the type formula ROOCRSCN in which R is a radical of a reduced and in allo-ocimene crotonaldehyde condensate which R is an aliphatic radical.

solublematerial from the product, for example,

and about 20%, with or withas used herein includes amples hereinbefore set forth are illustrative only, and that the invention as broadly described 7 of aliphatic radicals and aromatic 6. A thiocyanobutyrate of a reduced alloed from the group of metal thiocyanates, metal selenocyanates, and metal tellurocyanates which are at least partially soluble in the reaction mixture. I

11. A method for the production of the terpene compound described'in claim 1 which consists of reacting reduced allo-ocimen'e crotonaldehyde condensate with boxylic acid and then with a metal thiocyanate which is at least partially soluble in the reaction mixture. I I

12. -A method for the production of the terpene compound described in claim 1 which consists of reacting a reduced and-ocimene crotonaldehyde condensate with a halogenated aliphatic carboxylic acid anhydride and then with a metal thiocyanate which is at least partially soluble in the reaction mixture.

13. A method for the production of the terpene compound described in claim 1 which consists of reacting a reduced allo-ocimene.[crotonaldehyde condensate with a halogen substituted aliphatic acyl halide and then'witha metal thiocyanate which isat least partially soluble in the reaction mixture. t 1

14. A method for the production of the terpene compound described in claim 1 which consists of reacting a reduced allo-ocimene crotonaldehyde condensate-with a chlorinated lower fatty aci and then with an alkali metal thiocyanate.

15. A method for the production of the terpene compound described inclaim 1 which consists of reacting a reduced allo-ocimene crotonaldehyde condensate with a brominated lower fatty acid and then with an alkali metal thiocyanate.

JOSEPHN.BORGLIN.

a halogenated. aliphatic carreduced allo- 

